CN101840753B - Method for preparing high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin - Google Patents

Method for preparing high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin Download PDF

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CN101840753B
CN101840753B CN201010145849XA CN201010145849A CN101840753B CN 101840753 B CN101840753 B CN 101840753B CN 201010145849X A CN201010145849X A CN 201010145849XA CN 201010145849 A CN201010145849 A CN 201010145849A CN 101840753 B CN101840753 B CN 101840753B
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self
paste
argentalium
acrylate resin
silver
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CN101840753A (en
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沈良
王杰
宋锡瑾
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Hangzhou Dely Technology Co ltd
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HANGZHOU DELI TECHNOLOGY Co Ltd
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Abstract

The invention discloses a method for preparing high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin. The method comprises the following steps of: firstly selecting acrylate monomers, and preparing the self-crosslinking acrylate resin through solution polymerization; mixing ultrafine argentalium powder, lead-free glass powder with low melting point, a surface modifier, an auxiliary agent and a defoaming agent, and dispersing the mixture into the self-crosslinking acrylate resin; and repeatedly grinding the mixture to obtain the electronic argentalium paste. The method for preparing the high temperature sintering electronic argentalium paste has the characteristics of simple process, convenience and feasibility, no need of special equipment, less investment, easy control of product performance and the like.

Description

The preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin
Technical field
The present invention relates to a kind of preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin.
Background technology
Electric slurry is one type of important electron fine chemicals.Can be widely used in numerous industries such as electronics, information, communication, Aero-Space, computer, electrical equipment manufacturing, precision components and solar energy.Its manufacturing technology relates to association areas such as metallurgy, material, chemical industry, electronic technology and silk screen printing.Because the applied range of electric slurry, it is wide to develop related territory, product high in technological content, and therefore, the horizontal developed country of world industry relatively payes attention to the research and development of electric slurry product always.
In recent years; Along with the growing tension of conventional energy resources such as coal, oil, natural gas, it is extremely urgent to develop reproducible new forms of energy, and various countries furnish a huge amount of money for to develop various new forms of energy one after another; This wherein the development of solar energy attract attention and with the fastest developing speed with solar cell especially the most.According to statistics, global solar battery industry 1994-2004 increased by 17 times in 10 years, and manufacture of solar cells mainly is distributed in Japan, Europe and the U.S..The global solar battery scale of installing had reached 1744MW in 2006, grew up 19% than 2005, and the whole market output value formally breaks through 10,000,000,000 dollars of high pointes.The global solar battery production reached 3436MW in 2007, had increased by 56% than 2006.The output of global solar battery in 2008 is promoted to 6.85GW, also almost is the growth of multiple.Domestic research to solar cell is started in 1958, and at present, China has become the main manufacture of solar cells state in the whole world.National solar cell yield in 2007 is 1188MW, and output in 2008 continues to improve, and has reached 2,000,000 kilowatts.On industrial pattern; China's solar cell industry has formed certain situation of gathering; And between in March, 2009, ratified building the subsidy of installation photovoltaic generating system, to the photovoltaic generating system more than 500,000 kilowatts, every watt the highest payable 20 yuans (being roughly equal to 2.93 dollars).Because the Chinese government extremely payes attention to solar power generation.China is expected to as the U.S., can start a huge market.Solar energy power generating can occupy the important seat of world energy sources consumption in the near future, not only will substitute the part conventional energy resource, and will become the main body of world energy supplies.
Undoubtedly; Be accompanied by shooting up of photovoltaic industry; Demand to electric slurry also will increase sharply, and especially the thick-film electronic of high temperature sintering type silver aluminium paste is the main slurry that present electrode of solar battery uses; The market demand of following thick-film electronic slurry product will enlarge day by day, but domestic batch process to this series products is close to blank.Especially but aspect the high temperature sintering type thick-film electronic silver aluminium paste making of top grade, technology and market are almost completely by external monopolization.
Electric slurry is made up of conductive metal powder, low-melting glass powder, organic carrier and relevant auxiliary agent etc. usually.Wherein organic carrier often adopts polymer and other functional aid compositions such as epoxy resin, polyurethane, cellulose; Being the principal element that influences slurry thixotropy, anti-heavy property, levelability, volatility, printability, film forming thickness, slurry viscosity and bin stability etc., also is the key problem in technology that successfully prepares high temperature sintering type thick-film electronic silver aluminium paste.But because the solid content requirement of thick-film electronic silver aluminium paste is very high,, leaves for and utilize the leeway of secondary solvent adjusting slurry each item performance index little, cause pulp preparation regulation and control difficulty generally all more than 80%.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin.
The technical scheme that the present invention adopts is:
This method is at first selected acrylic ester monomer, through the solution polymerization self-crosslinking acrylate resin; Then wherein, through grinding repeatedly, make electronics silver aluminium paste with ultra-fine silver aluminium powder, low-melting point lead-less glasses powder end, surface modifier, auxiliary agent and antifoaming agent mixed and dispersed.
The preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin:
One, the step of self-crosslinking acrylate resin preparation is following:
1. in the agitated reactor of condenser is housed, add mass percent and be 35.0%~85.0% solvent, agitator also adds stand-by heat;
2. be that 15.0%~65.0% mix monomer adds in the mixing kettle with mass percent, add mass percent and be 0.1~0.5% initator and stir subsequent use;
When 3. solvent is warming up to 70~90 ℃ in the question response still, in agitated reactor, drip above-mentioned mix monomer, control whole mix monomers and in 1~3h, add, drip afterreaction 1~2h after, cooling, discharging, to obtain self-crosslinking acrylate resin subsequent use;
Two, take by weighing ultra-fine silver aluminium powder and low-melting point lead-less glasses powder, after mixing, add surface modifier and stir; Adding mass percent then is 10%~20% self-crosslinking acrylate resin; And auxiliary agent and antifoaming agent, through grinding 5~8h, get electronics silver aluminium paste after the filtration.
Described solvent is diethylene glycol (DEG) ether-ether or any two kinds of mixtures such as butyl carbitol, diethylene glycol dibutyl ether, diethylene glycol methyl ether acetate, DGDE acetate, butyl carbitol acetate.
Described mix monomer is any two kinds and a two or more mixture in methyl methacrylate, Isooctyl acrylate monomer, ethyl acrylate, butyl acrylate, GMA, N hydroxymethyl acrylamide, hydroxy-ethyl acrylate, this type of the hydroxypropyl acrylate acrylic compounds, and described initator is benzoyl peroxide or azodiisobutyronitrile.
The fineness of described silver and aluminium powder is 3~20 μ m, and the silver powder shape is spherical and sheet; Silver aluminium powder consumption is 65.0%~80.0% of a silver-colored aluminium paste total amount.
Described low-melting point lead-less glasses powder fineness is 3~20 μ m, and consumption is 5.0%~15.0% of a silver-colored aluminium paste total amount.
Described surface modifier is a silane coupler, and consumption is 0.5%~5.0% of a silver-colored aluminium paste total amount; Described auxiliary agent is terpinol or castor oil and dibutyl phthalate or dioctyl phthalate, and consumption is 0.5%~5.0% of a silver-colored aluminium paste total amount; Described antifoaming agent is tributyl phosphate or silicone oil, and consumption is 0.1%~0.5% of a silver-colored aluminium paste total amount.
The beneficial effect that the present invention has is:
1. given acrylate itself through selection function property monomer and had thixotroping, anti-heavy and suitable multiple functions such as levelability, further regulated electric slurry each item performance index for secondary solvent regulation and control leeway is provided.
2. because homemade acrylate has the self-crosslinking function, both slight network configuration can be formed, the secondary flow phenomenon of slurry when burning till can be effectively avoided in the temperature rise period in early stage of electric slurry sintering.
3. can be soft in the acrylate through regulating, the toughness of the proportional control polymer of hard monomer etc., avoided that ftractureing appears in electric slurry, the phenomenon of caving in when sintering.
Utilize method provided by the invention to prepare high temperature sintering electronic argentalium paste, it is simple, convenient and easy to have technology, need not special installation, to invest for a short time, and properties of product are convenient to characteristics such as control.
Embodiment
Embodiment 1:
At first, the adding mass percent is 38.0% butyl carbitol in the agitated reactor of condenser is housed, and agitator also adds stand-by heat; Then 39.0% methyl methacrylate, 5.0% Isooctyl acrylate monomer, 15.0% GMA, 3.0% N hydroxymethyl acrylamide are added in the mixing kettle, add 0.1% benzoyl peroxide and stir, subsequent use; When butyl carbitol is warming up to 75 ℃ in the question response still, in agitated reactor, be added dropwise to above-mentioned mix monomer, control in whole mix monomer 3h and add the acrylate that after 2h is reacted in continuation, cool off, discharging promptly gets self-cross linking type.Be that spherical silver powder 5%, flake silver powder 10.0%, aluminium powder 50.0% and the fineness of 3~20 μ m is that the low-melting point lead-less glasses powder 15.0% of 3~20 μ m adds in the mixer and mixes in addition with fineness; The silane coupler KH550 of adding 0.5%; The above-mentioned self-crosslinking acrylate resin 15.0% of back adding stirs; And terpinol 3.0%, dibutyl phthalate 1.0%, tributyl phosphate 0.5%; After mixing, place in the three-roll grinder through grinding 6h repeatedly, with promptly getting product after the filtration of 300 mesh filter screens.
Embodiment 2:
At first, the adding mass percent is 85.0% butyl carbitol acetate in the agitated reactor of condenser is housed, and agitator also adds stand-by heat; Then 8.0% methyl methacrylate, 2.0% butyl acrylate, 3.0% GMA, 1.0% N hydroxymethyl acrylamide, 1.0% hydroxy-ethyl acrylate are added in the mixing kettle; Add 0.3% azodiisobutyronitrile and stir, subsequent use; When butyl carbitol acetate is warming up to 85 ℃ in the question response still, in agitated reactor, be added dropwise to above-mentioned mix monomer, control in whole mix monomer 2.5h and add the acrylate that after 1h is reacted in continuation, cool off, discharging promptly gets self-cross linking type.Be that spherical silver powder 5.0%, flake silver powder 5.0%, aluminium powder 60% and the fineness of 3~20 μ m is that the low-melting point lead-less glasses powder 10.0% of 3~20 μ m adds in the mixer and mixes in addition with fineness; The silane coupler KH560 of adding 0.8%; The above-mentioned self-cross linking type multifunctional acrylic ester resin 16.0% of back adding stirs; And castor oil 2.5%, dioctyl phthalate 0.5%, silicone oil 0.2%; After mixing, place in the three-roll grinder through grinding 5h repeatedly, with promptly getting product after the filtration of 300 mesh filter screens.
Embodiment 3:
At first, in the agitated reactor of condenser is housed, adding mass percent is 25.0% diethylene glycol dibutyl ether, 25.0% diethylene glycol methyl ether acetate, and agitator also adds stand-by heat; Then 28.0% methyl methacrylate, 5.0% ethyl acrylate, 5.0% Isooctyl acrylate monomer, 10.0% GMA, 1.0% N hydroxymethyl acrylamide, 1.0% hydroxypropyl acrylate are added in the mixing kettle; Add 0.5% benzoyl peroxide and stir, subsequent use; When diethylene glycol (DEG) ether vinegar mixed solvent is warming up to 88 ℃ in the question response still, in agitated reactor, be added dropwise to above-mentioned mix monomer, control in whole mix monomer 2h and add the acrylate that after 2h is reacted in continuation, cool off, discharging promptly gets the self-crosslinkable type.Be that spherical silver powder 8.0%, flake silver powder 5.0%, aluminium powder 65% and the fineness of 3~20 μ m is that the low-melting point lead-less glasses powder 5.0% of 3~20 μ m adds in the mixer and mixes in addition with fineness; The silane coupler KH550 of adding 4.5%; The above-mentioned self-crosslinking acrylate resin 10.0% of back adding stirs; Terpinol 1.4%, dibutyl phthalate 1.0%, silicone oil 0.1% are after mixing; Place in the three-roll grinder through grinding 8h repeatedly, with promptly getting product after the filtration of 300 mesh filter screens.
Embodiment 4:
At first, in the agitated reactor of condenser is housed, adding mass percent is 25.0% diethylene glycol dibutyl ether, 25.0% DGDE acetate, and agitator also adds stand-by heat; Then 25.0% methyl methacrylate, 5.0% ethyl acrylate, 5.0% Isooctyl acrylate monomer, 3.0% N hydroxymethyl acrylamide, 10.0% GMA, 2.0% hydroxypropyl acrylate are added in the mixing kettle; Add 0.5% benzoyl peroxide and stir, subsequent use; When diethylene glycol (DEG) ether vinegar mixed solvent is warming up to 70 ℃ in the question response still, in agitated reactor, be added dropwise to above-mentioned mix monomer, control in whole mix monomer 2h and add the acrylate that after 2h is reacted in continuation, cool off, discharging promptly gets the self-crosslinkable type.Be that spherical silver powder 2.0%, flake silver powder 3.0%, aluminium powder 65% and the fineness of 3~20 μ m is that the low-melting point lead-less glasses powder 5.0% of 3~20 μ m adds in the mixer and mixes in addition with fineness; The silane coupler KH550 of adding 1.0%; The above-mentioned self-crosslinking acrylate resin 20.0% of back adding stirs; Terpinol 2.0%, dibutyl phthalate 1.5%, silicone oil 0.5% are after mixing; Place in the three-roll grinder through grinding 7h repeatedly, with promptly getting product after the filtration of 300 mesh filter screens.The technical indicator of the electronics silver aluminium paste product of above-mentioned 4 embodiment is as shown in the table:
Embodiment Fineness (order) Viscosity (mPas) Side's resistance (m Ω/) Sintering temperature (℃)
1 300 29000 16 750
2 300 28900 16 720
3 300 27800 18 700
4 300 28500 19 680

Claims (6)

1. the preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin, it is characterized in that: this method is at first selected acrylate monomer, through the solution polymerization self-crosslinking acrylate resin; Then with fineness be 3~20 μ m silver powder, aluminium powder, low-melting point lead-less glasses powder end, surface modifier, auxiliary agent and antifoaming agent mixed and dispersed wherein, through grinding repeatedly, make electronics silver aluminium paste;
Described acrylate monomer is methyl methacrylate, Isooctyl acrylate monomer, ethyl acrylate, butyl acrylate, GMA, N hydroxymethyl acrylamide, hydroxy-ethyl acrylate, hydroxypropyl acrylate;
One, the step of described self-crosslinking acrylate resin preparation is following:
1. in the agitated reactor of condenser is housed, add mass percent and be 35.0%~85.0% solvent, agitator also adds stand-by heat;
2. be that 15.0%~65.0% mix monomer adds in the mixing kettle with mass percent, add mass percent and be 0.1~0.5% initator and stir subsequent use;
When 3. solvent is warming up to 70~90 ℃ in the question response still, in agitated reactor, drip above-mentioned mix monomer, control whole mix monomers and in 1~3h, add, drip afterreaction 1~2h after, cooling, discharging, to obtain self-crosslinking acrylate resin subsequent use;
Described mix monomer is any two kinds and the two or more mixture in methyl methacrylate, Isooctyl acrylate monomer, ethyl acrylate, butyl acrylate, GMA, N hydroxymethyl acrylamide, hydroxy-ethyl acrylate, the hydroxypropyl acrylate compound;
Two, take by weighing silver powder, aluminium powder and low-melting point lead-less glasses powder, after mixing, add surface modifier and stir; Adding mass percent then is 10%~20% self-crosslinking acrylate resin; And auxiliary agent and antifoaming agent, through grinding 5~8h, get electronics silver aluminium paste after the filtration.
2. the preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin according to claim 1, it is characterized in that: described solvent is butyl carbitol, diethylene glycol dibutyl ether, diethylene glycol methyl ether acetate, DGDE acetate, butyl carbitol acetate or any two kinds of mixtures.
3. the preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin according to claim 1, it is characterized in that: described initator is benzoyl peroxide or azodiisobutyronitrile.
4. the preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin according to claim 1, it is characterized in that: described silver powder shape is spherical and sheet; Silver powder and aluminium powder consumption are 65.0%~80.0% of silver-colored aluminium paste total amount.
5. the preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin according to claim 1, it is characterized in that: described low-melting point lead-less glasses powder fineness is 3~20 μ m, and consumption is 5.0%~15.0% of a silver-colored aluminium paste total amount.
6. the preparation method of high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin according to claim 1, it is characterized in that: described surface modifier is a silane coupler, consumption is 0.5%~5.0% of a silver-colored aluminium paste total amount; Described auxiliary agent is terpinol or castor oil and dibutyl phthalate or dioctyl phthalate, and consumption is 0.5%~5.0% of a silver-colored aluminium paste total amount; Described antifoaming agent is tributyl phosphate or silicone oil, and consumption is 0.1%~0.5% of a silver-colored aluminium paste total amount.
CN201010145849XA 2010-04-13 2010-04-13 Method for preparing high temperature sintering electronic argentalium paste from self-crosslinking acrylate resin Expired - Fee Related CN101840753B (en)

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CN103022166A (en) * 2011-09-28 2013-04-03 杭州赛昂电力有限公司 Solar cell taking copper-clad aluminum wire as back electrode and producing process of solar cell
CN103021513A (en) * 2012-12-10 2013-04-03 滁州恒恩光电科技有限公司 Conducting silver aluminum slurry containing butyl acrylate

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1545111A (en) * 2003-11-26 2004-11-10 廖晓华 Conductive pulp for terminal electrode of chip capacitor
CN1655285A (en) * 2005-03-08 2005-08-17 东南大学 Photosensitive silver slurry for concentration electrode and method for preparing same
WO2006038652A1 (en) * 2004-10-06 2006-04-13 Zeon Corporation Electrode composition, electrode and battery
CN1933189A (en) * 2005-09-12 2007-03-21 中芯国际集成电路制造(上海)有限公司 New method of printing solar cell size

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1545111A (en) * 2003-11-26 2004-11-10 廖晓华 Conductive pulp for terminal electrode of chip capacitor
WO2006038652A1 (en) * 2004-10-06 2006-04-13 Zeon Corporation Electrode composition, electrode and battery
CN1655285A (en) * 2005-03-08 2005-08-17 东南大学 Photosensitive silver slurry for concentration electrode and method for preparing same
CN1933189A (en) * 2005-09-12 2007-03-21 中芯国际集成电路制造(上海)有限公司 New method of printing solar cell size

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Granted publication date: 20120822